4, 5, 6, 7-tetrachloro-3-imino-isoindoline-1-one derivatives



2,973,358 4,5,6,7-TETRACHLORO-S-IMINO-ISOINDOLINE- I-ONE DERIVATIVESAndr Pugin, Basel, Switzerland, assignor to J. R. Geigy A.-G., Basel,Switzerland No Drawing. Filed Dec. 24, 1957, Ser. No. 704,907 Claimspriority, application Switzerland July 13, 1956 13 Claims. (Cl. 260-240)The invention concerns new coloured condensation products which aredistinguished by their colour strength, their stability to heat, theirfastness to light and the fastness to migration of the coloured plasticsobtained therewith. The invention also concerns a production processwhich, by using new starting materials enables the coloured condensationproducts to be produced in greater purity and better yields than couldhave been attained by using the hitherto usual methods. The inventionconcerns, in addition, processes for the dyeing of organic material suchas paper and other types of cellulose, in particular however, processesfor pigmenting plastics and lacquers by the use of the new condensationproducts as well as the material dyed with the aid of these products.

It is known that by condensing 3-imino-isoindoline- 1 one, 3thio-isoindoline 1 one or 3 imino-isoindo line 1 thione and derivativesthereof substituted at the benzo radical with aromatic amines andhydrazines which, apart from the amino group or the hydrazino group,contain also a further amino or hydrazino group, a substituted amino orhydrazino group or another ring bound either direct or fused, coluoredcondensation products are obtained which are suitable for the dyeing ofcellulosic material such as paper, for the dyeing of lacquers as well asfor pigmenting plastics. In the known process, the substituent in the3-position is split off in the form of ammonia or hydrogen sulphide onheating the components alone or in inert organic solvents or diluentssuch as glacial acetic acid or alcohols and a G N- double linkage isformed between the amino nitrogen atom and the carbon atom in the3-position of the isoindoline-l-one ring. The coloured condensationproducts thus may be called azomethine dyes of the isoindoline-loneseries. However, condensation products which contain more than twosubstituents in the benzo radical of the isoindoline-l-one ring have notbeen known according to this process.

According to the present invention, however, it has now been found thatcondensation products obtained from dipn'mary amino compounds andisoindoline-l-ones which contain four halogen substituents in the benzoradical, are distinguished in the pure state from similar knowncompounds by particularly favourable fastness properties. For example,their colour is stronger, they are more fast to migration in plasticsand, in particular, more fast to light. They are obtained by condensingone mol of a diprimary amino compound with an amount equivalent to theprimary amino groups thereof of isoindoline-l-ones tetrahalogenated inthe benzo radical, which isoindolinel-ones contain substituents in the3-position which can be easily exchanged and which, according to type ornumber, occupy two linkages of the 3-positioned C-atom and are moremobile than doubly bound oxygen.

The new coloured condensation products correspond to the forumla:

Y IfiT (X)" Y o o Y \NH HN/ Y s Y o Y 3 t Y United States Patent C)wherein X represents the radical of an aromatic diamine, Y representshalogen and n represents the number 0 or 1.

The isoindoline-l-one derivatives used according to the presentinvention contain, according to the definition, four halogensubstituents in the benzene ring. Of technical importance areparticularly the tetrachloro compounds. Examples of the easily mobilesubstituents in the 3-position of the isoindoline-l-one compounds usedaccording to the present invention are the imino group =NH; 0rgani-.cally substituted imino groups =N-R, wherein R represents an alkyl,aralkyl, cycloalkyl or an iso or heterocyclic aryl radical for examplethe methyl, ethyl, butyl, hydroxyethyl, benzyl, cyclohexyl, phenyl,methylphenyl, chlorophenyl or 2-pyridyl group; two halogen substituentsor two tertiary amino groups.- These isoindoline-l-one derivatives morehighly halogen substituted in the benzo radical are new. a

Condensable 3-imino-isoindoline-1-one compounds according to a knownprocess may be obtained from phthalic acid anhydrides on heating innitrobenzene with urea and ammonium molybdate. However, it was foundthat the purity and yield of tetrahalogeno-3-imino-isoindolinel-oncs soproduced leaves much to be desired. The greatest drawback however,arises from the fact that the impurities may not easily be removed fromthe desired prod-, uct and unfavourably affect the purity and thefastness properties of the azomethine dyes produced therewith.Condensable tetrahalogeno-isoindoline-l-ones of high purity and easyaccessability are thus prerequisites in the process of manufacture ofthe instant azomethine dyes. New methods for'their manufacture aredisclosed in copending application Serial No. 769,310, filed October 24,1958, and in copending application Serial No. 769,311, also filedOctober 24, 1958, said applications having been divided out of thepresent application.

The following diprimary amino compounds can be used for example in theproduction of coloured condensation products according to the presentinvention: hydrazine and advantageously aromatic diprirnary aminocompounds of the isoor heterocyclic series, e.g. 1.3- and1.4-diaminobenzenes, 4.4'-diaminodiphenyl-and -triphenyl alkanes,4.4'-diaminodiphenylamines, 4.4'-diarnino-di-- phenyls,4.4"-diaminoterphenyls, 4.4'-diaminostilbenes, 1.4-, 1.5-, 1.7- and2.6-diaminonaphthalenes, 2.7-diamino-' fiuorenes, 1.4- and 1.5-diaminoanthraquinones, 2.6-di-.- amino pyridines, 2.7-diamino-carbazoles,2-(4-aminophenyl) 6-amino benzthiazoles, 2.6-diamino-benzthia zoles,2.5-bis-(4'-aminophenyl)-oxdiazoles and -thiadia-- zoles. Naturally,also isocyclic and heterocyclic aromatic diamines in which the aminogroups are in other positions can be used. Advantageously, however,diamino compounds are used in which the amino groups are in the.position of possible quinones. All aromatic rings can be still furthersubstituted, e.g. by alkyl groups such as methyl, ethyl, tert. butyl,tert. amyl groups, by ether groups such as methoxy, ethoxy, butoxy,phenoxy, methylmercapto, ethylmercapto, phenylmercapto groups, byhalogen atoms, by sulphonic acid and carboxylic acid groups,

their salts, esters and amides, by nitro, acylamino, sec-. ondary andtertiary amino groups. Particularly favourable for the colour strengthof the condensation products according to the present invention is thechoice oftsucht diprimary amino compounds which, on joining the isoin---doline-l-one rings, produce a system of conjugated double linkages.Examples of such diamino compounds are hydrazine, 1.4-diaminobenzene,l.4'-diaminodiphenyl and- 4.4'-diaminostilbene compounds as well asdiamino com-e pounds of more highly condensed isocyclic or heterovcyclic structures in which the amino groups take the posi tions ofpossible quinones. The list given above contains some examples of suchdiamino compounds. Of technical interest are the 1.3- and1.4-diaminobenzene, 4.4- diaminodiphenyl, 4.4'-diaminostilbenederivatives and the diaminonaphthylene derivatives corresponding toquinones, also the derivatives of 4.4'-diaminodiphenyl compounds which,by ring-forming linking members, are further condensed to formfluorenes, diphenylenoxides, diphenylene sulphides, diphenylenesulphones, carbazolcs. The fact that they can be further substituted inthe aromatic rings is common to all these compounds.

As is apparent from the preceding description, the preferred objects ofthe present invention are compounds of the above general formula,wherein Y is chloro and X stands for a 1.3- or 1.4-phenylene, a 1.4-,1.5-, 1.7- or 2.6- naphthylene, a 4.4'-diphenylene and a 4.4'-stilbyleneradical.

The condensation of the aforesaid diprimary amino compounds with thereactive tetrahalogeno-isoindoline-1- ones substituted in the 3-positionby either two halogen atoms, preferably an imino or substituted iminogroup, possibly also by either sulphur or two tertiary amino groups,proceeds very quickly and easily often even in the cold, possibly onwarming the well mixed components, particularly advantageously in thepresence of inert organic solvents and dliuents such as hydrocarbons,halogenated hydrocarbons, aliphatic or alicyclic ethers and ketones oresters. toluene, xylenes, tetraline, naphthalene, diphenyl, carbontetrachloride, tetrachloroethylene, chlorobenzene, diandtri-chlorobenzene, nitrobenzene, dibutyl ether, dioxan, diphenyl ether,acetone, cyclohexanone can be used as inert solvents. It is possible toperform the condensation in the presence of acid binding agents such assodium acetate, magnesium oxide or calcium carbonate. Also organicnitrogen bases may possibly be used, e.g. pyridine, quinoline or dialkylanilines.

Insofar as they are compounds having no acid, saltforming groups, thecoloured condensation products according to the present invention arevery difficultly soluble substances. They precipitate from the solutionof the components already while hot and can easily be purified byfiltering off and washing with organic solvents, water,

aqueous alkalies and aqueous acids. If starting materials are used whichcontain acid salt-forming groups, e.g. sulphonic acid or carboxylgroups, the condensation is performed advantageously in organic/aqueoussolution. Yellow, orange, red, brown, violet to black condensationproducts are obtained according to the diamine used. Insofar as they areinsoluble in water, due to their excellent fastness to light, theircolour strength and fastness to migration in plastics, such as polyvinylchloride, they are valuable pigment dyestuffs which are excellentlysuited for pigmenting lacquers, polymeric synthetic materials andrubber. In finely dispersed form, they can also be used for the dyeingof paper or for the dyeing of viscose or cellulose esters or polyamidesin the spinning mass. If they contain water solubilising, salt-forminggroups, they can be converted into insoluble dye lacquers with the earthalkali, earth or heavy metal salts usual for this purpose or, dependingon the ailinity, they can be used for the dyeing of cellulosic materialsuch as paper, cellulose fibres or animal fibres.

' Because of the mild reaction conditions prevailing in some of theprocesses of manufacture of condensable4.5.6.7-tetrahalogenoisoindoline-l-ones as described, it is possible toperform the intermediate and azomethine dye production in a one batchprocess, as hereinafter described e.g. in Example 7. For example1.3.3.4.5.6.7-heptachloro-isoindolenine can be reacted in an inertorganic solvent such as chlorobenzene with one molecular proportion ofan alcohol such as ethanol at room temperature. Then a polyprimary aminocompound can be added advantageously mixed with a tertiary amine such aspyridine or triethylamine; If the reaction mixture is then boiled Forexample, cyclohexane, benzene,

the desired azomethine dye of the isoindoline-l-one series separatesimmediately. Also the 3.4.5.6-tetrachloro-2- cyanobenzene-l-carboxylicacid lower alkyl or benzyl esters may be treated in inert organicsolvents with dry ammonia at room temperature to form the condeusable 3-imino-4.5.6.7-tetrachloro-isoindoline-l-ones and then the diprimaryaromatic amines such as 4.4'-diaminodiphenyl compounds may be added. Onboiling the reaction mixture the desired azomethine dyes separate andcan be isolated by hot filtration and washing with organic solvents,aqueous acids, aqueous alkalies and pure water.

The following examples illustrate the invention which is acontinuation-in-part of my copending application Ser. No. 669,928, filedJuly 5, 1957 (and which has been abandoned since the filing of thepresent application). Where not otherwise stated, parts are given asparts by weight. The temperatures are in degrees centigrade.

Example 1 A solution of 5.4 parts of 1.4-diaminobenzene in 200 parts ofo-dichlorobenzene is added to a solution of 34 parts of33.4.5.6.7-hexachloro-isoindoline-1-one in 300 parts ofo-dichlorobenzene. The yellow suspension which immediately forms is thenheated for 3 hours at 160-170" whereupon it is filtered hot and theresidue is washed with o-dichlorobenzene, alcohol and acetone. 32 partsof a pure, strongly coloured, orange-yellow pigment are obtained whichis distinguished by excellent fastness to light, migration and solvents.

The 3.3.4.5.6.7-hexachloro-isoindoline-l-one is produced by heating 1mol of tetrachlorophthalin'iide with 1.2 mol of phosphorus pentachloridein chlorobenzene for 1 hour at First the unchangedtetrachlorophthalimide is filtered oil but whereupon, on cooling, thenew hexachloro-indoline-l-one crystallises out. After recrystallisingfrom benzene, it melts at 205-206" on decomposition.

Calculated for C HONCI N, 4.11. Found: N, 4.27.

Yellow pigments having similar good properties are obtained if in thisexample, the 1.4-diaminobenzene is re, placed by 7.4 parts of1.4-diaminonaphthalene or by 10.6 parts of 4.4'-diaminoazobenzene.

An even more red pigment having the same good properties is obtained ifin this example the 1.4-diaminobenzene is replaced by 12.15 parts of3.3'-dichlorobenzidino. More greenish pigments having very good fastnessproperties are also obtained if in this example, the 1.4-diaminobenzeneis replaced by 5.4 parts of 1.3-diaminobenzene, 6.1 parts of1-methyl-2.6-diaminobenzene, 12.3 parts of2.7-diamino-dibenzothiophene-1.1-dioxide or 11.5 parts of4.4'-diamino-3-nitrodiphenyl.

Example 2 A cold solution of 1.84 parts of 4.4'-diaminodiphenyl in 200parts of benzene is added to a solution of 6.8 parts of3.3.4.S.6.7-hexachloro-isoindoline-l-one in 200 parts of benzene. Anorange precipitate forms immediately. The whole is stirred for 1 hour atroom temperature, the pigment is filtered oif and washed with benzene,acetone and water. The pure orange pigment can be recrystallised from agreat deal of nitrobenzene and melts at over 360". It has excellentfastness to light as well as very good fastness to migration, solvents,cross-lacquering, oil, acid and alkali.

Example 3 6.6 parts of 3.3'-dichloro-4.4-diaminodiphenyl chlorohydrateare heated for half an hour at 200 with 11.6 parts of3-imino-4.5.6.7-tetrachloro-isoindoline-l-one in 200 parts ofnitrobenzene. The yellow-brown pigment formed is filtered ofl hot fromthe nitrobenzene, washed with alcohol, water and acetone. It has goodfastness to migration and light. The3-imino-4.5.6.7-tetrachloroisoindoline-l-one is produced by heating 1mol of tetrachlorophthalic acid anhydride and 4 mol of urea in thepresence of $4 mol of ammonium molybdate in nitrobenzene at The notquite pure reaction product a melts on decomposition around 305; itprovides a not quite pure pigment.

Example 4 A solution of 6.8 parts of3.3.4.5.6.7-hexachloro-isoindoline-l-one in 100 parts of xylene isrefluxed for 2 hours with a solution of 2.44 parts of4.4'-diamino-3.3'-dimethoxydiphenyl in 100 parts of xylene. The pigmentis filtered oil and washed with alcohol. It is a yellowish-red pigmentwhich has very good fastness properties. If this pigment is again heatedfor 1 hour at 200 in 100 parts of nitrobenzene, it becomes bluish redand its already very good fastness to light is more noticeably improved.

Example 5 A solution of 10.6 parts of 4.4'-diamino-3.3-dimethyldiphenylin 150 parts of o-dichlorobenzene and a solution of 35 parts of3.3.4.5.6.7-hexachloro-isoindoline-l-one in 500 parts ofo-dichlorobenzene are heated for 3 hours at 160-170 while stirring. Theprecipitate is filtered oflf hot, washed with alcohol and acetone and,after drying, 34 parts of a pure red pigment are obtained which has verygood fastnes to oil, acid, alkali, solvents, migration and light.

=Red pigments having the same good properties are also obtained if inthis example, 7.4 parts of 1.5-diaminonaphthalene or. 10.5 parts of4.4'-diaminostilbene are used instead of4.4'-diamino-3.3'-dimethyldiphenyl.

Example 6 14.2 parts of 3-imino-4.5.6.7-tetrachloro-isoindoline-1- oneand 4.6 parts of 4.4'-diaminodiphenyl are refluxed for 2 hours in 300parts of glacial acetic acid. A pure orange pigment is formed which isfiltered oil and purified by washing with glacial acetic acid, alcoholand acetone. The pigment is identical to that of Example 2.

The 3-iminio-4.5.6.7-tetrachloro-isoindoline-l-one used above isobtained by reacting 34 parts of 3.3.4.5.6.7-hexachloro-isoindoline-l-one with 60 parts of aqueous ammonia. It is apale yellowish powder which melts at Example 7 6.6 parts of1.3.3.4.5.6.7-heptachloro-isoindolenine are dissolved in 80 parts ofdioxan and the solution is added to a solution of 2 parts of4.4'-diaminodiphenyl chlorohydrate in 300 parts of water. The suspensionis heated to 80, the orange pigment is filtered oil and washed withalcohol and acetone. It can be recrystallised from nitrobenzene and isthen identical to the pigment produced according to Example 2.

Example 8 3.4 parts of 3.3.4.5.6.7-hexachloro-isoindoline-1-one and 1part of hydrazine hydrate are heated to 100 for 5 minutes in 100 partsof chlorobenzene. The greenishyellow pigment which precipitates isfiltered off hot and washed with acetone and water. It is distinguishedby its purity and its excellent fastness to migration and light.

Example 9 1.58 parts of pyridine are added to 6.8 parts of 3.3.4.5.6.7-hexachloro-isoindoline-l-one in l00 parts of dioxan. A whiteprecipitate immediately forms. A solu- 3.3.4.5.6.7-hexachloro-isoindoline-l-one with di-n butyl tion of 1.84 parts of4.4-diaminodiphenyl in 50 parts of dioxan is added whereupon thesuspension turns first yellow and then orange. After heating for 2 hoursat 95, the orange pigment is filtered off and washed with alcohol andwater. It; has excellent fastness to light.

Example 10 The solution of a mixture of 1.84 parts of4.4'-diaminodiphenyl and 2.53 parts of 3.3-dichlorobenzidine in parts ofo-dichlorobenzene is added to a solution of 13.2 parts of3.3.4.5.6.7-hexachloro-isoindoline-l-one in 200 parts ofo-dichlorobenzene. The orange suspension formed is heated for an hour at170, the precipitate is filtered off and washed with acetone. Thepigment thus obtained is more yellow but has the same good fastnessproperties as that of Example 2.

Example 11 2.38 parts of 1.5-diamino anthraquinone are dissolved in'100parts -of'hot nitrobenzene and condensed for 2 hours'at 140 with 6.6parts of 3.3.4.5.6.7-hexachloroisoindoline-l-one dissolved in 100 partsof nitrobenzene. The pigment which has been filtered oil is stirredagain for 1 hour at 200 in 100 parts of nitrobenzene, filtered ofi hotand washed with alcohol and acetone. The pigment so obtained isblue-black and is distinguished by 'its good fastness properties and itscolour strength.

Example 12 v .13 parts of 3.3.4.5.6.7-hexachloro-isoindoline-l-one areheated with 2.2 parts of 2.6-diaminopyridine in 200 parts ofo-dichlorobenzen for 2 hours at 170. The yellow pigment is filtered 01fhot and washed with alcohol. It has good fastness to acid, alkali, oiland light.

Example 13 142.5 parts of tetrachlorophthalimide and parts of phosphoruspentachloride in 500 parts of chlorobenzene are heated for 1 hour at Asolution of 48 parts of 4.4'-diaminodiphenyl in 300 parts ofchlorobenzene is added and the whole is stirred for 2 hours at 125. 300parts of ethanol are added to the suspension, the pigment is filteredoff, washed with alcohol, acetone, diluted ammonia solution and waterand dried. This crude pigment is again purified by boiling out withnitrobenzene and filtering hot. The pigment is orange and has good fastness to migration and light.

Example 14 17.2 parts of 3.3.4.5.6.7-hexachloro-isoindoline-l-one aredissolved in 250 parts of benzene. This solution is mixed with asolution of 4.6 parts of 4.4'-diaminodiphenyl in 200 parts of benzeneand 8 parts of pyridine and the whole is refluxed for 1 hour. A pureorange pigment is formed which is filtered oil under suction and washedwith alcohol and water.

Also 10.1 parts of triethylamine can be used in this example instead ofpyridine.

Example 15 4.41 parts of3.3-bis-morpho1ino-4.5.6.7-tetrachloroisoindoline-l-one (M.P. 211-212",produced by reacting 3.3.4.5.6.7-hexachloro-isoindoline-l-one withmorpholine in benzene), are heated for 5 minutes at 100 with 0.92 partof 4.4'-diaminodiphenyl in 50 parts of glacial acetic acid. Afterfiltering and washing the residue with glacial acetic acid and water, anorange pigment is isolated which has excellent fastness properties. j

An orange pigment having similar good properties is obtained if in thisexample, the 3.3-bis-morpholino- 4.5.6.7-tetrachloro-isoindoline-l-oneis replaced by 5.25 parts of 3.3-bis dibutylamino-4.5.6.7-tetrachloro-isoindoline-l-one. This latter compound isproduced by reacting amine in benzene.

7 Example 16 2.96 partsof 2.S-bis-(4'-aminophenyl) -oxadiazole and 6.8parts of 3.3.4.5.6.7-hexachloro-isoindoline-l-one in 100 parts ofo-dichlorobenzene are heated for 2 hours in a vacuum at 120 under 90 mm.Hg pressure. After filtering olf and washing the residue with alcohol,acetone and water, a pure yellow pigment is obtained which has excellentfastness to light and migration.

If, instead of 2.5-bis-(4'-aminophenyl)-oxadiazole, 3.20 parts of2.5-bis-(3'-methyl-4'-aminophenyl)-oxadiazole are used, then a morereddish pigment which has similar good properties is obtained.

Pigments having still more red shades are obtained if in this examplethe 2.5-bis-(4'-aminophenyl)-oxadiazole is replaced by '3.12 parts of2.5-bis-(4-aminophenyl)-thiadiazole or by 3.8 parts of2.5-bis-(3'-chloro- 4'-aminophenyl)-thiadiazole.

Example 17 10 parts of the pigment obtained according to Example 1 from1.4-diaminobenzene, 10 parts of hydrate of alumina, 30 parts of linseedoil varnish of medium viscosity and 0.2 part of cobalt linoleate aremixed and rubbed in a three-roll mill. A graphic colour is obtainedwhich produces reddish-yellow prints of particular purity and colourstrength and, in addition, has excellent fastness to solvents, acid,alkali and light.

Example 18 10 parts of the pigment obtained according to Example 2, 10parts of titanium dioxide, 35 parts of a 60% solution of a modified ureaalkyd resin in xylene/butanol 1:1, 10 parts of turpentine oil and partsof xylene are milled for 45 hours in a ball mill. After pouring ontoaluminium sheets and annealing for one hour at 120, a pure orange dyeingis obtained which has excellent fastness properties, in particular verygood fastness to cross-lacquering.

Example 19 wherein =NX-N= stands for di-irninoaryl of which theindicated nitrogen atoms are aromatically bound.

2. A compound which corresponds to the general formula:

01 Y 01 o o 01- 01 NH HN/ c1 O/ o 01 u n o 0 wherein =N--Y-N= representsdi-iminophenyl.

3. A, compound which corresponds to the general.

formula:

l a it ll 01 wherein =NZ --N= represents di-iminonaphthyl.

4. A' compound; which corresponds to the general formula:

wherein .=N-V'--N.= represents bis-p-iminophenyl.

5. A compound which corresponds to the general formula:

01-? C/ \G 5 2% 21 wherein 10 12. The compound of the formula:

9. The compound of the formula:

N II C C ll II C' m N C C 0 m p .w m H .m m m e .m H fi w m m H o m o md ll C m. m m m c N C C 0 k e m m B 1 C C m m m m m A .v m N C C 0 a m mC N m n .m e m .m m n d m C N m N C C 0 m m 0 1 UNITED STATES PATENTS2,537,352 Jones Jan. 9, 1951 2,692,267 Campbell Oct. 19, 1954 2,701,252Vollrnan et a1. Feb. 1, 1955 FOREIGN PATENTS 11. The compound of theformula:

945,782 Germany July 19, 1956 615,697 Great Britain Ian. 10, 1949 OTHERREFERENCES Ind. and Eng. Chem., vol. 39, No. 11, p. 1420 (1947).

Elvidge et aL: J. Chem. Society (1952), pp. 5000-5007.

Clark et a] J Chem Society (1953), pp 3593-3601 OCH:

OCH:

5. A COMPOUND WHICH CORRESPONDS TO THE GENERAL FORMULA: